Don't You Want Me by The Human League is featured in Blame It on the Alcohol, the fourteenth episode of Season Two. It is sung by Blaine and Rachel. They perform this song on the stage in Rachel's basement after a drunk kiss during a game of "Spin the Bottle" at The Rachel Berry House Party Train Wreck Extravaganza.

Rachel drunkenly announces that her new duet partner will be Blaine, and leans into a noticeably disturbed Kurt, laughing hysterically. During the song, Mercedes sits and watches them happily, Tina and Mike are both dance crazily, Santana and Sam kiss while Quinn looks jealous, Brittany and Artie cuddle with each other and make out, and Lauren and Puck hug each other. After this song, Rachel considers that she likes Blaine on a higher level than friendship, and decides to act on it.